Compressibility and Dielectric Relaxation of Mixtures of Water with Monohydroxy Alcohols

Isentropic compressibility data and principal dielectric relaxation times, mostly for normal alcohols and for mixtures of monohydroxy alcohols with water, are evaluated and compared to one another. It is found that the microdynamics of the liquids, as reflected by the dielectric relaxation times, can be generally explained in the light of a defect diffusion model. Within the framework of that model, the principal relaxation time is predominantly controlled by the local concentration of hydrogen bonding sites. The alkyl groups of the alcohols are shown to have a 2-fold influence by reducing the concentration of the H-bonding sites and by also contributing to the activation enthalpy of relaxation. The effect of alkyl groups on the compressibility is quite different. The compressibility of methanol exceeds that of water by a substantial amount. Within the series of normal alcohols, in correspondence with the behavior of normal alkanes, the liquids become less compressible with increasing alkyl chain length. Relative molal shifts Bκ and Bd of the compressibility and dielectric relaxation time, respectively, of dilute solutions of alcohols in water are consistent with the behavior of aqueous solutions of other organic solutes. The Bd values increase with hydrophobic character of the solute (ΔBd = 0.045 (mol/kg)(-1) for an additional methyl group per solute molecule or organic ion), whereas Bκ decreases (ΔBκ = -0.012 (mol/kg)(-1)). Reduced orientational mobility combined with decreased compressibility appears to be characteristic of hydration shells around hydrophobic solutes.